Generation of trifluoromethyl-substituted pyrrolo[3,2-c]quinolines via a copper(II)-catalyzed tandem reaction of N-(σ-iodoaryl)alkynylimines with 2-isocyanoacetates is reported. The process involves a [3 + 2] cycloaddition and intramolecular C-C bond coupling, leading to the fluorine-containing N-heterocycles under mild conditions with high efficiency.